AT246747B - Process for the preparation of an L-lyxopyranosyl halide - Google Patents
Process for the preparation of an L-lyxopyranosyl halideInfo
- Publication number
- AT246747B AT246747B AT433862A AT433862A AT246747B AT 246747 B AT246747 B AT 246747B AT 433862 A AT433862 A AT 433862A AT 433862 A AT433862 A AT 433862A AT 246747 B AT246747 B AT 246747B
- Authority
- AT
- Austria
- Prior art keywords
- lyxopyranosyl
- methyl
- halide
- preparation
- cyclocarbonato
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- -1 L-lyxopyranosyl halide Chemical class 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 239000007858 starting material Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GRTGGSXWHGKRSB-UHFFFAOYSA-N dichloromethyl methyl ether Chemical compound COC(Cl)Cl GRTGGSXWHGKRSB-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- QJIHWLIDFLBEKN-UHFFFAOYSA-N 4,7-dihydroxy-8-methyl-3-phenyldiazenylchromen-2-one Chemical compound O=C1OC=2C(C)=C(O)C=CC=2C(O)=C1N=NC1=CC=CC=C1 QJIHWLIDFLBEKN-UHFFFAOYSA-N 0.000 description 1
- YJQPYGGHQPGBLI-UHFFFAOYSA-N Novobiocin Natural products O1C(C)(C)C(OC)C(OC(N)=O)C(O)C1OC1=CC=C(C(O)=C(NC(=O)C=2C=C(CC=C(C)C)C(O)=CC=2)C(=O)O2)C2=C1C YJQPYGGHQPGBLI-UHFFFAOYSA-N 0.000 description 1
- IPDFDKLAMGJMAY-AEQNFAKKSA-N O[C@H]1COC(Cl)[C@H](O)[C@@H]1O Chemical compound O[C@H]1COC(Cl)[C@H](O)[C@@H]1O IPDFDKLAMGJMAY-AEQNFAKKSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YJQPYGGHQPGBLI-KGSXXDOSSA-N novobiocin Chemical compound O1C(C)(C)[C@H](OC)[C@@H](OC(N)=O)[C@@H](O)[C@@H]1OC1=CC=C(C(O)=C(NC(=O)C=2C=C(CC=C(C)C)C(O)=CC=2)C(=O)O2)C2=C1C YJQPYGGHQPGBLI-KGSXXDOSSA-N 0.000 description 1
- 229960002950 novobiocin Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
<Desc/Clms Page number 1>
Verfahren zur Herstellung eines L-Lyxopyranosylhalogenids
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines L-Lyxopyranosylhalogenids der allgemeinen Formel
EMI1.1
in der die Substituenten R Alkylgruppen mit 1-4 Kohlenstoffatomen darstellen, und ist dadurch gekennzeichnet, dass man auf ein 5, 5-Dialkyl-4-0-alkyl-2, 3-cyclocarbonato-alkyl-L-lyxopyranosid Dichlor- dimethyläther in Gegenwart einer Lewis-Säure einwirken lässt.
Unter Lewis-Säuren sind hier Halogenide von Metallen der II., III. und IV. Gruppe des periodischen Systems, darunter insbesondere Zinkchlorid, zu verstehen.
Cyclocarbonato-L-lyxopyranosylhalogenide sind neue Verbindungen, welche als Zwischenprodukte für die Synthese von Novobiocin und Novobiocin-ähnlichen Verbindungen verwendet werden können.
Das 5, 5-Dimethyl-4-0-methyl-2, 3-cyclocarbonato-L-lyxopyranosylchlorid ist eine bevorzugte Ausgangssubstanz. Sie kann dadurch hergestellt werden, dass man auf das bekannte 5, 5-Dimethyl-4-0-methyl- 2, 3-cyclocarbonato-methyl-L-lyxopyranosid Dichlordimethyläther in Gegenwart einer Lewis-Säure einwirken lässt.
Die erfindungsgemässe Umsetzung wird zweckmässigerweise so durchgeführt, dass man das MethylL-lyxopyranosid in frisch destilliertem asymmetrischem Dichlordimethyläther löst und durch Zugabe katalytischer Mengen einer Lewis-Säure, z. B. frisch geschmolzenem Zinkchlorid, die Bildung des L-Lyxopyranosylchlorids beschleunigt.
Beispiel : 2, 5 g 5, 5-Dimethyl-4-0-methyl-2, 3-cyclocarbonato-methyl-L-lyxopyranosid werden in 6 ml frisch hergestelltem 1, 1-Dichlordimethyläther in Gegenwart von 20 mg frisch geschmolzenem, fein pulverisiertem Zinkchlorid auf dem Dampfbad langsam erwärmt. Nach 30 min wird das Reaktionsgemisch bei einer Badtemperatur von 40 C unter vermindertem Druck eingedampft. Letzte Spuren von 1, 1-Dichlordi- methyläther werden durch Abdampfen mit absolutem Benzol entfernt. Der ölige Rückstand wird in Benzol gelöst und mit eisenfreier Aktivkohle entfärbt. Der nach Abtreiben des Lösungsmittels hinterbleibende Rückstand besteht aus 5, 5-Dimethyl-4-0-methyl-2, 3-cyclocarbonato-L-lyxopyranosylchlorid.
Der erhaltene ölige Chlorzucker kann durch folgende Reaktion charakterisiert werden : 3, 0 g 3-Phenylazo-4, 7-dihydroxy-8-methyl-cumarin werden in einem 250 ml-Rundkolben in 40 ml frisch destilliertem Chinolin aufgeschlämmt. In dieses Gemisch werden nach Zugabe von 2, 5 g frisch
EMI1.2
<Desc/Clms Page number 2>
Die über Natriumsulfat getrocknete Lösung wird eingedampft, das zurückbleibende benzollösliche rote Öl wird an 60 g akt. Magnesiumsilikat adsorbiert. Die mit Benzol/Essigester (95 : 5) eluierte Fraktion liefert nach Eindampfen und Umkristallisieren des Rückstandes'in Essigester/Petroläther reines 3-Phenyl-
EMI2.1
-oe- (5, 5-dimethyl-4-0-methyl-2, 3-cyc1ocarbonato - L-lyxopyranosyloxy) -8-methyl-cumarinPATENTANSPRÜCHE : 1.
Verfahren zur Herstellung eines L-Lyxopyranosylhalogenids der allgemeinen Formel
EMI2.2
in der die Substituenten R Alkylgruppen mit 1-4 Kohlenstoffatomen darstellen und Hal ein Halogenatom bezeichnet, dadurch gekennzeichnet, dass man auf ein 5, 5-Dialkyl-4-0-alkyl-2, 3-cyclocarbonato- alkyl-L-lyxopyranosid Dichlordimethyläther in Gegenwart einer Lewis-Säure einwirken lässt.
<Desc / Clms Page number 1>
Process for the preparation of an L-lyxopyranosyl halide
The present invention relates to a process for the preparation of an L-lyxopyranosyl halide of the general formula
EMI1.1
in which the substituents R represent alkyl groups with 1-4 carbon atoms, and is characterized in that a 5, 5-dialkyl-4-0-alkyl-2, 3-cyclocarbonato-alkyl-L-lyxopyranoside dichlorodimethyl ether in the presence a Lewis acid can act.
Lewis acids here are halides of metals of II., III. and IV. group of the periodic table, including in particular zinc chloride.
Cyclocarbonato-L-lyxopyranosyl halides are new compounds which can be used as intermediates for the synthesis of novobiocin and novobiocin-like compounds.
The 5, 5-dimethyl-4-0-methyl-2, 3-cyclocarbonato-L-lyxopyranosyl chloride is a preferred starting substance. It can be produced by letting dichlorodimethyl ether act on the known 5,5-dimethyl-4-0-methyl-2,3-cyclocarbonato-methyl-L-lyxopyranoside in the presence of a Lewis acid.
The inventive reaction is conveniently carried out by dissolving the methyl L-lyxopyranoside in freshly distilled asymmetric dichlorodimethyl ether and adding catalytic amounts of a Lewis acid, e.g. B. freshly melted zinc chloride, the formation of L-lyxopyranosyl chloride accelerates.
Example: 2.5 g of 5, 5-dimethyl-4-0-methyl-2, 3-cyclocarbonato-methyl-L-lyxopyranoside are added to 6 ml of freshly prepared 1,1-dichlorodimethyl ether in the presence of 20 mg of freshly melted, finely powdered Zinc chloride slowly warmed up on the steam bath. After 30 min, the reaction mixture is evaporated at a bath temperature of 40 ° C. under reduced pressure. The last traces of 1,1-dichlorodimethyl ether are removed by evaporation with absolute benzene. The oily residue is dissolved in benzene and decolorized with iron-free activated carbon. The residue that remains after the solvent has been driven off consists of 5,5-dimethyl-4-0-methyl-2,3-cyclocarbonato-L-lyxopyranosyl chloride.
The oily chlorosugar obtained can be characterized by the following reaction: 3.0 g of 3-phenylazo-4, 7-dihydroxy-8-methyl-coumarin are suspended in 40 ml of freshly distilled quinoline in a 250 ml round bottom flask. In this mixture, after adding 2.5 g, fresh
EMI1.2
<Desc / Clms Page number 2>
The solution, dried over sodium sulfate, is evaporated, the remaining benzene-soluble red oil is acted on 60 g. Magnesium silicate adsorbed. The fraction eluted with benzene / ethyl acetate (95: 5) gives, after evaporation and recrystallization of the residue in ethyl acetate / petroleum ether, pure 3-phenyl
EMI2.1
-oe- (5, 5-dimethyl-4-0-methyl-2, 3-cyc1ocarbonato - L-lyxopyranosyloxy) -8-methyl-coumarin
Process for the preparation of an L-lyxopyranosyl halide of the general formula
EMI2.2
in which the substituents R represent alkyl groups with 1-4 carbon atoms and Hal denotes a halogen atom, characterized in that a 5, 5-dialkyl-4-0-alkyl-2, 3-cyclocarbonato-alkyl-L-lyxopyranoside dichlorodimethyl ether in Can act presence of a Lewis acid.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH246747X | 1960-11-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AT246747B true AT246747B (en) | 1966-05-10 |
Family
ID=4465746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AT433862A AT246747B (en) | 1960-11-07 | 1961-10-31 | Process for the preparation of an L-lyxopyranosyl halide |
Country Status (1)
| Country | Link |
|---|---|
| AT (1) | AT246747B (en) |
-
1961
- 1961-10-31 AT AT433862A patent/AT246747B/en active
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